The objective of this research program is the development of new methods for the control of stereochemistry by asymmetric induction. A variety of new techniques has already been uncovered, including the ene reaction of chiral glyoxylates and N-sulfinyl carbamates, and the cycloaddition reactions of a variety of substituted, chiral esters. Several of these methods permit control at two or three chiral centers, with some flexibility in reaction conditions and/or substrates for selection between the possible diastereomers. The more firmly developed of these processes are being implemented in the synthesis of biologically active molecules, and continued efforts in this direction are anticipated as additional information is gained on the newer transformations. The program also has as its objective the further development of an empirically based system for the assignment of stereochemistry to acyclic systems. Preliminary investigations in this area provide predictions of carbon 13 shift effects due to stereochemical differences that are quite close to observations. It is anticipated that as additional data is collected and further refinements are made to the method that exceptionally reliable correlations between stereochemistry and/or conformational preferences will be possible in complex systems.